Process for making light guides with extraction structures and light guides produced thereby

ABSTRACT

A process comprises imagewise exposing at least a portion of a photoreactive composition to light sufficient to cause simultaneous absorption of at least two photons/thereby inducing at least one acid- or radical-initiated chemical reaction where the composition is exposed to the light, the imagewise exposing being carried out in a pattern that is effective to define at least the surface of a plurality of light extraction structures. Each one of the array of light extraction structures has at least one shape factor; the shape factor may vary across the array. At least one light extraction structure may have the geometric configuration of a truncated asphere.

STATEMENT OF PRIORITY

This application claims the priority of U.S. Provisional Application No.60/747,609 filed May 18, 2006, the contents of which are herebyincorporated by reference.

FIELD

This invention relates to processes for making light extractionstructures, light extraction structure arrays, and/or light extractionstructure array masterforms and, in other aspects, to light extractionstructures, light extraction structure arrays, and/or light extractionstructure array masterforms made thereby. This invention further relatesto light guides comprising the light extraction structure arrays and toarticles comprising the light guides.

BACKGROUND

A variety of devices have been proposed for illuminating electronicdisplays and keypads. These devices include backlighting panels, frontlighting panels, concentrators, reflectors, structured-surface films,and other optical devices for redirecting, collimating, distributing, orotherwise manipulating light. Passive optical components (for example,lenses, prisms, mirrors, and light extraction structures) are well-knownand are used in optical systems to collect, distribute, or modifyoptical radiation.

Efficient use of light is particularly important in battery poweredelectronic displays and keypads such as those used in cell phones,personal digital assistants, and laptop computers. By improving lightingefficiency, battery life can be increased and/or battery sizes can bereduced. Prismatic films are commonly used to improve lightingefficiency and enhance the apparent brightness of a backlit liquidcrystal display, and multiple light sources (for example, light emittingdiodes (LEDs)) are commonly used for this purpose in keypads.

Lighting quality is also an important consideration in electronicdisplays and keypads. One measure of lighting quality for a backlitdisplay or keypad is brightness uniformity. Because displays (and, to asomewhat lesser extent, keypads) are typically studied closely or usedfor extended periods of time, relatively small differences in thebrightness can easily be perceived. These types of variances inbrightness can be distracting or annoying to a user. To soften or masknon-uniformities, a light scattering element (for example, a diffuser)can sometimes be used. However, such scattering elements can negativelyaffect the overall brightness of a display or keypad.

Multiple light sources can alternatively be used to achieve brightnessuniformity, but this approach has the associated disadvantage of reducedbattery life. Thus, there has been some attention to the development ofvarious means of effectively distributing the light from a more limitednumber of light sources, including the development of light guidescomprising a plurality of light extraction structures. Such lightextraction structures, as well as light extraction structure arrays,have been made by a number of different techniques, each having adifferent set of strengths and weaknesses.

SUMMARY

Thus, we recognize that there is a need for processes that can be usedto fabricate light guides that can meet the quality, cost, and/orperformance requirements of a variety of different applications. Inparticular, we recognize a need for processes that are capable ofproducing light extraction structures and light extraction structurearrays that can be used to provide efficient light guides enablingbrightness uniformity and long battery life (or reduced battery size).

Briefly, in one aspect, this invention provides a process for making alight extraction structure array or a light extraction structure arraymasterform. The process comprises providing a photoreactive composition,the photoreactive composition comprising (a) at least one reactivespecies that is capable of undergoing an acid- or radical-initiatedchemical reaction, and (b) at least one multiphoton photoinitiatorsystem. The reactive species is preferably a curable species (morepreferably, a curable species selected from the group consisting ofmonomers, oligomers, and reactive polymers). At least a portion of thecomposition can be imagewise exposed to light sufficient to causesimultaneous absorption of at least two photons, thereby inducing atleast one acid- or radical-initiated chemical reaction where thecomposition is exposed to the light.

The imagewise exposing can be carried out in a pattern that is effectiveto define at least the surface of an array of light extractionstructures, each of the light extraction structures having at least oneshape factor, and the array of light extraction structures having adistribution that can be uniform or non-uniform. Generally, thedistribution can be non-uniform and/or the shape factor of at least onelight extraction structure can be different from that of at least oneother light extraction structure.

The composition can, optionally, be developed by removing the resultingexposed portion, or the resulting non-exposed portion, of thecomposition. Optionally, after imagewise exposing at least a portion ofthe composition, at least a portion of the composition can benonimagewise exposed to light sufficient to effect reaction of at leasta portion of any remaining unreacted photoreactive composition.

Preferably, the distribution of the array is non-uniform, and at leastone shape factor (preferably, height) varies at least somewhat(preferably, regularly) across (or as a function of position within) thearray of light extraction structures. Shape factors can be said to bedifferent when the height (or another dimension) and/or the geometricconfiguration of at least one light extraction structure is differentfrom that of at least one other light extraction structure in the array.Geometric configurations can be said to be different when two lightextraction structures in the array cannot be scaled to besuperimposable. Preferably, the areal density of the array of lightextraction structures varies across the array and/or at least one shapefactor varies across the array (more preferably, both areal density andat least one shape factor vary across the array: even more preferably,both areal density and height vary across the array; most preferably,areal density increases as the height of the light extraction structuresincreases across the array).

It has been discovered that multiphoton photofabrication processes canbe well-suited for fabricating light extraction structure arrays havingvarying optical properties (for example, arrays exhibiting a spatialvariation of light extraction). Surprisingly, the process of theinvention can provide flexibility and control in producing a variety ofindividual light extraction structure profiles in a single array, yetcan be used to achieve desirably low levels of average surface roughnesswhile maintaining industrially acceptable fabrication speeds or“throughput.” Such flexibility and control can also facilitate theproduction of arrays of varying fill factor and/or varying degrees ofdistribution uniformity.

The process of the invention involves the use of relatively low-costmaterials (for example, polymers) and is capable of relatively easyintegration into the fabrication processes used in the manufacture ofoptoelectronic devices. The process also enables cost-effectivereplication (for example, through the production of masterforms).Furthermore, the process is capable of flexibly and controllablyproducing light extraction structures of various different geometricconfigurations and heights (that is, different shape factors) and arraysof various different symmetries (or asymmetries) and fill factors, eachsuch type of light extraction structure and light extraction structurearray thereby having different, controlled optical properties.

Thus, at least some embodiments of the process of the invention meet theabove-stated need for light extraction structure array fabricationprocesses that can satisfy the quality, cost, and/or performancerequirements of a variety of different applications and also, inparticular, provide efficient light guides enabling brightnessuniformity and long battery life (or reduced battery size). Lightextraction structure arrays made by the process of the invention can besuitable for use in numerous optical applications including, forexample, in backlit displays and backlit keypads.

In other aspects, this invention also provides:

a light extraction structure array comprising a plurality of lightextraction structures having a non-uniform distribution, each of thelight extraction structures having a principal axis and at least oneshape factor, and the plurality of light extraction structuresexhibiting a variation in areal density, in at least one shape factor,and in principal axis across the plurality of light extractionstructures;

a light extraction structure array comprising a plurality of lightextraction structures having a non-uniform distribution, each of thelight extraction structures having a geometric configuration, and thegeometric configuration of at least one of the light extractionstructures being a truncated asphere;

light guides comprising the arrays; and

optical devices (for example, a backlit display or a backlit keypad)comprising the light guides.

BRIEF DESCRIPTION OF DRAWING

These and other features, aspects, and advantages of the presentinvention will become better understood with regard to the followingdescription, appended claims, and accompanying drawing, wherein:

FIG. 1 is a schematic representation of an exemplary multiphotonphotofabrication system useful for carrying out the process of theinvention.

FIG. 2 is a scanning electron micrograph (a side view) of an embodimentof the light extraction structure array of the invention, whichembodiment was produced by the process of the invention and is describedin Example 1 below.

FIGS. 3 a-3 d show side sectional views of exemplary light extractionstructures that can be produced by carrying out embodiments of theprocess of the invention, the light extraction structures each having atleast one shape factor including a geometric configuration.

FIG. 3 a shows a light extraction structure 10 having an asphericgeometric configuration 12;

FIG. 3 b shows a light extraction structure 10 having a truncatedaspheric geometric configuration 14;

FIG. 3 c shows a light extraction structure 10 having a conic geometricconfiguration 16; and

FIG. 3 d shows a light extraction structure 10 having a truncated conicgeometric configuration 18.

FIGS. 4 a and 4 b show top plan views of exemplary light guides that canbe produced by carrying out embodiments of the process of the invention.

FIG. 4 a shows a light guide 30 comprising an array 20 having anon-uniform distribution of light extraction structures 10.

FIG. 4 b shows a light guide 30 comprising an array 20 having a uniformdistribution of light extraction structures 10.

These figures, which are idealized, are not drawn to scale and areintended to be merely illustrative and nonlimiting.

DETAILED DESCRIPTION

Definitions

As used in this patent application:

“average surface roughness” means the average deviation between theactual surface profile of a light extraction structure and its averagesurface profile;

“cure” means to effect polymerization and/or to effect crosslinking;

“electronic excited state” means an electronic state of a molecule thatis higher in energy than the molecule's electronic ground state, that isaccessible via absorption of electromagnetic radiation, and that has alifetime greater than 10⁻¹³ seconds;

“exposure system” means an optical system plus a light source;

“fill factor” (in regard to a light extraction structure array) meansthe portion or percentage of the area of the array that modifiesincident actinic radiation;

“light extraction structure” means a microstructure (having a length,width, and height of at least about one micrometer) that is capable ofdirecting or distributing light (for example, a protruding or recessedmicrostructure that distributes light within and/or directs light from alight guide);

“masterform” means an originally-fabricated article that can be used tomanufacture a tool for replication;

“multiphoton absorption” means simultaneous absorption of two or morephotons to reach a reactive, electronic excited state that isenergetically inaccessible by the absorption of a single photon of thesame energy;

“optical system” means a system for controlling light, the systemincluding at least one element chosen from refractive optical elementssuch as lenses, reflective optical elements such as mirrors, anddiffractive optical elements such as gratings. Optical elements shallalso include diffusers, waveguides, and other elements known in theoptical arts;

“photochemically effective amounts” (of the components of thephotoinitiator system) means amounts sufficient to enable the reactivespecies to undergo at least partial reaction under the selected exposureconditions (as evidenced, for example, by a change in density,viscosity, color, pH, refractive index, or other physical or chemicalproperty);

“photosensitizer” means a molecule that lowers the energy required toactivate a photoinitiator by absorbing light of lower energy than isrequired by the photoinitiator for activation and interacting with thephotoinitiator to produce a photoinitiating species therefrom;

“shape factor” (in regard to a light extraction structure) means adimension (length, width, or height) or the geometric configuration ofthe structure; and

“simultaneous” means two events that occur within the period of 10⁻¹⁴seconds or less;

“sufficient light” means light of sufficient intensity and appropriatewavelength to effect multiphoton absorption; and

“three-dimensional light pattern” means an optical image wherein thelight energy distribution resides in a volume or in multiple planes andnot in a single plane.

Reactive Species

Reactive species suitable for use in the photoreactive compositionsinclude both curable and non-curable species. Curable species aregenerally preferred and include, for example, addition-polymerizablemonomers and oligomers and addition-crosslinkable polymers (such asfree-radically polymerizable or crosslinkable ethylenically-unsaturatedspecies including, for example, acrylates, methacrylates, and certainvinyl compounds such as styrenes), as well as cationically-polymerizablemonomers and oligomers and cationically-crosslinkable polymers (whichspecies are most commonly acid-initiated and which include, for example,epoxies, vinyl ethers, cyanate esters, etc.), and the like, and mixturesthereof.

Suitable ethylenically-unsaturated species are described, for example,by Palazzotto et al. in U.S. Pat. No. 5,545,676 at column 1, line 65,through column 2, line 26, and include mono-, di-, and poly-acrylatesand methacrylates (for example, methyl acrylate, methyl methacrylate,ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearylacrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate,ethyleneglycol diacrylate, diethyleneglycol diacrylate,triethyleneglycol dimethacrylate, 1,3-propanediol diacrylate,1,3-propanediol dimethacrylate, trimethylolpropane triacrylate,1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate,pentaerythritol triacrylate, pentaerythritol tetraacrylate,pentaerythritol tetramethacrylate, sorbitol hexacrylate,bis[1-(2-acryloxy)]-p -ethoxyphenyldimethylmethane,bis[1-(3-acryloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane,trishydroxyethyl-isocyanurate trimethacrylate, the bis-acrylates andbis-methacrylates of polyethylene glycols of molecular weight about200-500, copolymerizable mixtures of acrylated monomers such as those ofU.S. Pat. No. 4,652,274, and acrylated oligomers such as those of U.S.Pat. No. 4,642,126); unsaturated amides (for example, methylenebis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylenebis-acrylamide, diethylene triamine tris-acrylamide andbeta-methacrylaminoethyl methacrylate); vinyl compounds (for example,styrene, diallyl phthalate, divinyl succinate, divinyl adipate, anddivinyl phthalate); and the like; and mixtures thereof. Suitablereactive polymers include polymers with pendant (meth)acrylate groups,for example, having from 1 to about 50 (meth)acrylate groups per polymerchain. Examples of such polymers include aromatic acid (meth)acrylatehalf ester resins such as Sarbox™ resins available from Sartomer (forexample, Sarbox™ 400, 401, 402, 404, and 405). Other useful reactivepolymers curable by free radical chemistry include those polymers thathave a hydrocarbyl backbone and pendant peptide groups withfree-radically polymerizable functionality attached thereto, such asthose described in U.S. Pat. No. 5,235,015 (Ali et al.). Mixtures of twoor more monomers, oligomers, and/or reactive polymers can be used ifdesired. Preferred ethylenically-unsaturated species include acrylates,aromatic acid (meth)acrylate half ester resins, and polymers that have ahydrocarbyl backbone and pendant peptide groups with free-radicallypolymerizable functionality attached thereto.

Suitable cationically-reactive species are described, for example, byOxman et al. in U.S. Pat. Nos. 5,998,495 and 6,025,406 and include epoxyresins. Such materials, broadly called epoxides, include monomeric epoxycompounds and epoxides of the polymeric type and can be aliphatic,alicyclic, aromatic, or heterocyclic. These materials generally have, onthe average, at least 1 polymerizable epoxy group per molecule(preferably, at least about 1.5 and, more preferably, at least about 2).The polymeric epoxides include linear polymers having terminal epoxygroups (for example, a diglycidyl ether of a polyoxyalkylene glycol),polymers having skeletal oxirane units (for example, polybutadienepolyepoxide), and polymers having pendant epoxy groups (for example, aglycidyl methacrylate polymer or copolymer). The epoxides can be purecompounds or can be mixtures of compounds containing one, two, or moreepoxy groups per molecule. These epoxy-containing materials can varygreatly in the nature of their backbone and substituent groups. Forexample, the backbone can be of any type and substituent groups thereoncan be any group that does not substantially interfere with cationiccure at room temperature. Illustrative of permissible substituent groupsinclude halogens, ester groups, ethers, sulfonate groups, siloxanegroups, nitro groups, phosphate groups, and the like. The molecularweight of the epoxy-containing materials can vary from about 58 to about100,000 or more.

Other epoxy-containing materials that are useful include glycidyl ethermonomers of the formula

where R′ is alkyl or aryl and n is an integer of 1 to 8. Examples areglycidyl ethers of polyhydric phenols obtained by reacting a polyhydricphenol with an excess of a chlorohydrin such as epichlorohydrin (forexample, the diglycidyl ether of2,2-bis-(2,3-epoxypropoxyphenol)-propane). Additional examples ofepoxides of this type are described in U.S. Pat. No. 3,018,262, and inHandbook of Epoxy Resins, Lee and Neville, McGraw-Hill Book Co., NewYork (1967).

A number of commercially available epoxy monomers or resins can be used.Epoxides that are readily available include, but are not limited to,octadecylene oxide; epichlorohydrin; styrene oxide; vinylcyclohexeneoxide; glycidol; glycidyl methacrylate; diglycidyl ethers of bisphenol A(for example, those available under the trade designations “EPON 815C”,“EPON 813”, “EPON 828”, “EPON 1004F”, and “EPON 1001F” from HexionSpecialty Chemicals, Inc., Columbus, Ohio); and diglycidyl ether ofbisphenol F (for example, those available under the trade designations“ARALDITE GY281” from Ciba Specialty Chemicals Holding Company, Basel,Switzerland, and “EPON 862” from Hexion Specialty Chemicals, Inc.).Other aromatic epoxy resins include the SU-8 resins available fromMicroChem. Corp., Newton, Mass.

Other exemplary epoxy monomers include vinyl cyclohexene dioxide(available from SPI Supplies, West Chester, Pa.); 4-vinyl-1-cylcohexenediepoxide (available from Aldrich Chemical Co., Milwaukee, Wis.);3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate (for example,one available under the trade designation “CYRACURE UVR-6110” from DowChemical Co., Midland, Mich.);3,4-epoxy-6-methylcylcohexylmethyl-3,4-epoxy-6-methyl-cylcohexanecarboxylate;2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane;bis(3,4-epoxycyclohexylmethyl) adipate (for example, one available underthe trade designation “CYRACURE UVR-6128” from Dow Chemical Co.);bis(3,4-epoxy-6-methylclyclohexylmethyl)adipate;3,4-epoxy-6-methylcyclohexane carboxylate; and dipentene dioxide.

Still other exemplary epoxy resins include epoxidized polybutadiene (forexample, one available under the trade designation “POLY BD 605E” fromSartomer Co., Inc., Exton, Pa.); epoxy silanes (for example,3,4-epoxycylclohexylethyltrimethoxysilane and3-glycidoxypropyltrimethoxysilane, commercially available from AldrichChemical Co., Milwaukee, Wis.); flame retardant epoxy monomers (forexample, one available under the trade designation “DER-542”, abrominated bisphenol type epoxy monomer available from Dow Chemical Co.,Midland, Mich.); 1,4-butanediol diglycidyl ether (for example, oneavailable under the trade designation “ARALDITE RD-2” from CibaSpecialty Chemicals); hydrogenated bisphenol A-epichlorohydrin basedepoxy monomers (for example, one available under the trade designation“EPONEX 1510” from Hexion Specialty Chemicals, Inc.); polyglycidyl etherof phenol-formaldehyde novolak (for example, one available under thetrade designation “DEN-431” and “DEN-438” from Dow Chemical Co.); andepoxidized vegetable oils such as epoxidized linseed and soybean oilsavailable under the trade designations “VIKOLOX” and “VIKOFLEX” fromAtofina Chemicals (Philadelphia, Pa.).

Additional suitable epoxy resins include alkyl glycidyl etherscommercially available from Hexion Specialty Chemicals, Inc. (Columbus,Ohio) under the trade designation “HELOXY”. Exemplary monomers include“HELOXY MODFIER 7” (a C₈-C₁₀ alky glycidyl ether), “HELOXY MODIFIER 8”(a C₁₂-C₁₄ alkyl glycidyl ether), “HELOXY MODIFIER 61” (butyl glycidylether), “HELOXY MODIFER 62” (cresyl glycidyl ether), “HELOXY MODIFER 65”(p-tert-butylphenyl glycidyl ether), “HELOXY MODIFER 67” (diglycidylether of 1,4-butanediol), “HELOXY 68” (diglycidyl ether of neopentylglycol), “HELOXY MODIFER 107” (diglycidyl ether ofcyclohexanedimethanol), “HELOXY MODIFER 44” (trimethylol ethanetriglycidyl ether), “HELOXY MODIFIER 48” (trimethylol propanetriglycidyl ether), “HELOXY MODIFER 84” (polyglycidyl ether of analiphatic polyol), and “HELOXY MODIFER 32” (polyglycol diepoxide).

Other useful epoxy resins comprise copolymers of acrylic acid esters ofglycidol (such as glycidyl acrylate and glycidyl methacrylate) with oneor more copolymerizable vinyl compounds. Examples of such copolymers are1:1 styrene-glycidyl methacrylate and 1:1 methyl methacrylate-glycidylacrylate. Other useful epoxy resins are well known and contain suchepoxides as epichlorohydrins, alkylene oxides (for example, propyleneoxide), styrene oxide, alkenyl oxides (for example, butadiene oxide),and glycidyl esters (for example, ethyl glycidate).

Useful epoxy-functional polymers include epoxy-functional silicones suchas those described in U.S. Pat. No. 4,279,717 (Eckberg et al.), whichare commercially available from the General Electric Company. These arepolydimethylsiloxanes in which 1-20 mole % of the silicon atoms havebeen substituted with epoxyalkyl groups (preferably, epoxycyclohexylethyl, as described in U.S. Pat. No. 5,753,346 (Leir et al.).

Blends of various epoxy-containing materials can also be utilized. Suchblends can comprise two or more weight average molecular weightdistributions of epoxy-containing compounds (such as low molecularweight (below 200), intermediate molecular weight (about 200 to 1000),and higher molecular weight (above about 1000)). Alternatively oradditionally, the epoxy resin can contain a blend of epoxy-containingmaterials having different chemical natures (such as aliphatic andaromatic) or functionalities (such as polar and non-polar). Othercationically-reactive polymers (such as vinyl ethers and the like) canadditionally be incorporated, if desired.

Preferred epoxies include aromatic glycidyl epoxies (for example, theEPON resins available from Hexion Specialty Chemicals, Inc. and the SU-8resins available from MicroChem. Corp., Newton, Mass., including XP KMPR1050 strippable SU-8), and the like, and mixtures thereof. Morepreferred are the SU-8 resins and mixtures thereof.

Suitable cationally-reactive species also include vinyl ether monomers,oligomers, and reactive polymers (for example, methyl vinyl ether, ethylvinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether,triethyleneglycol divinyl ether (RAPI-CURE DVE-3, available fromInternational Specialty Products, Wayne, N.J.), trimethylolpropanetrivinyl ether, and the VECTOMER divinyl ether resins from Morflex,Inc., Greensboro, N.C. (for example, VECTOMER 1312, VECTOMER 4010,VECTOMER 4051, and VECTOMER 4060 and their equivalents available fromother manufacturers)), and mixtures thereof. Blends (in any proportion)of one or more vinyl ether resins and/or one or more epoxy resins canalso be utilized. Polyhydroxy-functional materials (such as thosedescribed, for example, in U.S. Pat. No. 5,856,373 (Kaisaki et al.)) canalso be utilized in combination with epoxy- and/or vinylether-functional materials.

Non-curable species include, for example, reactive polymers whosesolubility can be increased upon acid- or radical-induced reaction. Suchreactive polymers include, for example, aqueous insoluble polymersbearing ester groups that can be converted by photogenerated acid toaqueous soluble acid groups (for example,poly(4-tert-butoxycarbonyloxystyrene). Non-curable species also includethe chemically-amplified photoresists described by R. D. Allen, G. M.Wallraff, W. D. Hinsberg, and L. L. Simpson in “High Performance AcrylicPolymers for Chemically Amplified Photoresist Applications,” J. Vac.Sci. Technol. B, 9, 3357 (1991). The chemically-amplified photoresistconcept is now widely used for microchip manufacturing, especially withsub-0.5 micron (or even sub-0.2 micron) features. In such photoresistsystems, catalytic species (typically hydrogen ions) can be generated byirradiation, which induces a cascade of chemical reactions. This cascadeoccurs when hydrogen ions initiate reactions that generate more hydrogenions or other acidic species, thereby amplifying reaction rate. Examplesof typical acid-catalyzed chemically-amplified photoresist systemsinclude deprotection (for example, t-butoxycarbonyloxystyrene resists asdescribed in U.S. Pat. No. 4,491,628, tetrahydropyran (THP)methacrylate-based materials, THP-phenolic materials such as thosedescribed in U.S. Pat. No. 3,779,778, t-butyl methacrylate-basedmaterials such as those described by R. D Allen et al. in Proc. SPIE2438, 474 (1995), and the like); depolymerization (for example,polyphthalaldehyde-based materials); and rearrangement (for example,materials based on the pinacol rearrangements).

If desired, mixtures of different types of reactive species can beutilized in the photoreactive compositions. For example, mixtures offree-radically-reactive species and cationically-reactive species arealso useful.

Photoinitiator System

The photoinitiator system is a multiphoton photoinitiator system, as theuse of such a system enables polymerization to be confined or limited tothe focal region of a focused beam of light. Such a system preferably isa two- or three-component system that comprises at least one multiphotonphotosensitizer, at least one photoinitiator (or electron acceptor),and, optionally, at least one electron donor. Such multi-componentsystems can provide enhanced sensitivity, enabling photoreaction to beeffected in a shorter period of time and thereby reducing the likelihoodof problems due to movement of the sample and/or one or more componentsof the exposure system.

Preferably, the multiphoton photoinitiator system comprisesphotochemically effective amounts of (a) at least one multiphotonphotosensitizer that is capable of simultaneously absorbing at least twophotons and that, optionally but preferably, has a two-photon absorptioncross-section greater than that of fluorescein; (b) optionally, at leastone electron donor compound different from the multiphotonphotosensitizer and capable of donating an electron to an electronicexcited state of the photosensitizer; and (c) at least onephotoinitiator that is capable of being photosensitized by accepting anelectron from an electronic excited state of the photosensitizer,resulting in the formation of at least one free radical and/or acid.

Alternatively, the multiphoton photoinitiator system can be aone-component system that comprises at least one photoinitiator.Photoinitiators useful as one-component multi-photon photoinitiatorsystems include acyl phosphine oxides (for example, those sold by Cibaunder the trade name Irgacure™ 819, as well as 2,4,6 trimethyl benzoylethoxyphenyl phosphine oxide sold by BASF Corporation under the tradename Lucirin™ TPO-L) and stilbene derivatives with covalently attachedsulfonium salt moeties (for example, those described by W. Zhou et al.in Science 296, 1106 (2002)). Other conventional ultraviolet (UV)photoinitiators such as benzil ketal can also be utilized, althoughtheir multi-photon photoinitiation sensitivities will generally berelatively low.

Multiphoton photosensitizers, electron donors, and photoinitiators (orelectron acceptors) useful in two- and three-component multiphotonphotoinitiator systems are described below.

(1) Multiphoton Photosensitizers

Multiphoton photosensitizers suitable for use in the multiphotonphotoinitiator system of the photoreactive compositions are those thatare capable of simultaneously absorbing at least two photons whenexposed to sufficient light. Preferably, the photosensitizers have atwo-photon absorption cross-section greater than that of fluorescein(that is, greater than that of 3′,6′-dihydroxyspiro[isobenzofuran-1(3H),9′-[9H]xanthen]3-one). Generally, the preferred cross-section can begreater than about 50×10⁻⁵⁰ cm⁴ sec/photon, as measured by the methoddescribed by C. Xu and W. W. Webb in J. Opt. Soc. Am. B, 13, 481 (1996)(which is referenced by Marder and Perry et al. in InternationalPublication No. WO 98/21521 at page 85, lines 18-22).

More preferably, the two-photon absorption cross-section of thephotosensitizer is greater than about 1.5 times that of fluorescein (or,alternatively, greater than about 75×10⁻⁵⁰ cm⁴ sec/photon, as measuredby the above method); even more preferably, greater than about twicethat of fluorescein (or, alternatively, greater than about 100×10⁻⁵⁰ cm⁴sec/photon); most preferably, greater than about three times that offluorescein (or, alternatively, greater than about 150×10⁻⁵⁰ cm⁴sec/photon); and optimally, greater than about four times that offluorescein (or, alternatively, greater than about 200×10⁻⁵⁰ cm⁴sec/photon).

Preferably, the photosensitizer is soluble in the reactive species (ifthe reactive species is liquid) or is compatible with the reactivespecies and with any binders (as described below) that are included inthe composition. Most preferably, the photosensitizer is also capable ofsensitizing 2-methyl-4,6-bis(trichloromethyl)-s-triazine undercontinuous irradiation in a wavelength range that overlaps the singlephoton absorption spectrum of the photosensitizer (single photonabsorption conditions), using the test procedure described in U.S. Pat.No. 3,729,313.

Preferably, a photosensitizer can also be selected based in part uponshelf stability considerations. Accordingly, selection of a particularphotosensitizer can depend to some extent upon the particular reactivespecies utilized (as well as upon the choices of electron donor compoundand/or photoinitiator).

Particularly preferred multiphoton photosensitizers include thoseexhibiting large multiphoton absorption cross-sections, such asRhodamine B (that is,N-[9-(2-carboxyphenyl)-6-(diethylamino)-3H-xanthen-3-ylidene]-N-ethylethanaminiumchloride or hexafluoroantimonate) and the four classes ofphotosensitizers described, for example, by Marder and Perry et al. inInternational Patent Publication Nos. WO 98/21521 and WO 99/53242. Thefour classes can be described as follows: (a) molecules in which twodonors are connected to a conjugated π (pi)-electron bridge; (b)molecules in which two donors are connected to a conjugated π(pi)-electron bridge which is substituted with one or more electronaccepting groups; (c) molecules in which two acceptors are connected toa conjugated π (pi)-electron bridge; and (d) molecules in which twoacceptors are connected to a conjugated π (pi)-electron bridge which issubstituted with one or more electron donating groups (where “bridge”means a molecular fragment that connects two or more chemical groups,“donor” means an atom or group of atoms with a low ionization potentialthat can be bonded to a conjugated π (pi)-electron bridge, and“acceptor” means an atom or group of atoms with a high electron affinitythat can be bonded to a conjugated π (pi)-electron bridge).

The four above-described classes of photosensitizers can be prepared byreacting aldehydes with ylides under standard Wittig conditions or byusing the McMurray reaction, as detailed in International PatentPublication No. WO 98/21521.

Other compounds are described by Reinhardt et al. (for example, in U.S.Pat. Nos. 6,100,405, 5,859,251, and 5,770,737) as having largemultiphoton absorption cross-sections, although these cross-sectionswere determined by a method other than that described above.

Preferred photosensitizers include the following compounds (and mixturesthereof):

(2) Electron Donor Compounds

Electron donor compounds useful in the multiphoton photoinitiator systemof the photoreactive compositions are those compounds (other than thephotosensitizer itself) that are capable of donating an electron to anelectronic excited state of the photosensitizer. Such compounds may beused, optionally, to increase the multiphoton photosensitivity of thephotoinitiator system, thereby reducing the exposure required to effectphotoreaction of the photoreactive composition. The electron donorcompounds preferably have an oxidation potential that is greater thanzero and less than or equal to that of p-dimethoxybenzene. Preferably,the oxidation potential is between about 0.3 and 1 volt vs. a standardsaturated calomel electrode (“S.C.E.”).

The electron donor compound is also preferably soluble in the reactivespecies and is selected based in part upon shelf stabilityconsiderations (as described above). Suitable donors are generallycapable of increasing the speed of cure or the image density of aphotoreactive composition upon exposure to light of the desiredwavelength.

When working with cationically-reactive species, those skilled in theart will recognize that the electron donor compound, if of significantbasicity, can adversely affect the cationic reaction. (See, for example,the discussion in U.S. Pat. No. 6,025,406 (Oxman et al.) at column 7,line 62, through column 8, line 49.)

In general, electron donor compounds suitable for use with particularphotosensitizers and photoinitiators can be selected by comparing theoxidation and reduction potentials of the three components (asdescribed, for example, in U.S. Pat. No. 4,859,572 (Farid et al.)). Suchpotentials can be measured experimentally (for example, by the methodsdescribed by R. J. Cox, Photographic Sensitivity, Chapter 15, AcademicPress (1973)) or can be obtained from references such as N. L. Weinburg,Ed., Technique of Electroorganic Synthesis Part II Techniques ofChemistry, Vol. V (1975), and C. K. Mann and K. K. Barnes,Electrochemical Reactions in Nonaqueous Systems (1970). The potentialsreflect relative energy relationships and can be used to guide electrondonor compound selection.

Suitable electron donor compounds include, for example, those describedby D. F. Eaton in Advances in Photochemistry, edited by B. Voman et al.,Volume 13, pp. 427-488, John Wiley and Sons, New York (1986); by Oxmanet al. in U.S. Pat. No. 6,025,406 at column 7, lines 42-61; and byPalazzotto et al. in U.S. Pat. No. 5,545,676 at column 4, line 14through column 5, line 18. Such electron donor compounds include amines(including triethanolamine, hydrazine, 1,4-diazabicyclo[2.2.2]octane,triphenylamine (and its triphenylphosphine and triphenylarsine analogs),aminoaldehydes, and aminosilanes), amides (including phosphoramides),ethers (including thioethers), ureas (including thioureas), sulfinicacids and their salts, salts of ferrocyanide, ascorbic acid and itssalts, dithiocarbamic acid and its salts, salts of xanthates, salts ofethylene diamine tetraacetic acid, salts of (alkyl)_(n)(aryl)_(m)borates(n+m=4) (tetraalkylammonium salts preferred), various organometalliccompounds such as SnR₄ compounds (where each R is independently chosenfrom among alkyl, aralkyl (particularly, benzyl), aryl, and alkarylgroups) (for example, such compounds as n-C₃H₇Sn(CH₃)₃, (allyl)Sn(CH₃)₃,and (benzyl)Sn(n-C₃H₇)₃), ferrocene, and the like, and mixtures thereof.The electron donor compound can be unsubstituted or can be substitutedwith one or more non-interfering substituents. Particularly preferredelectron donor compounds contain an electron donor atom (such as anitrogen, oxygen, phosphorus, or sulfur atom) and an abstractablehydrogen atom bonded to a carbon or silicon atom alpha to the electrondonor atom.

Preferred amine electron donor compounds include alkyl-, aryl-, alkaryl-and aralkyl-amines (for example, methylamine, ethylamine, propylamine,butylamine, triethanolamine, amylamine, hexylamine, 2,4-dimethylaniline,2,3-dimethylaniline, o-, m- and p-toluidine, benzylamine, aminopyridine,N,N′-dimethylethylenediamine, N,N′-diethylethylenediamine,N,N′-dibenzylethylenediamine, N,N′-diethyl-1,3-propanediamine,N,N′-diethyl-2-butene-1,4-diamine, N,N′-dimethyl-1,6-hexanediamine,piperazine, 4,4′-trimethylenedipiperidine, 4,4′-ethylenedipiperidine,p-N,N-dimethyl-aminophenethanol and p-N-dimethylaminobenzonitrile);aminoaldehydes (for example, p-N,N-dimethylaminobenzaldehyde,p-N,N-diethylaminobenzaldehyde, 9-julolidine carboxaldehyde, and4-morpholinobenzaldehyde); and aminosilanes (for example,trimethylsilylmorpholine, trimethylsilylpiperidine,bis(dimethylamino)diphenylsilane, tris(dimethylamino)methylsilane,N,N-diethylaminotrimethylsilane, tris(dimethylamino)phenylsilane,tris(methylsilyl)amine, tris(dimethylsilyl)amine,bis(dimethylsilyl)amine, N,N-bis(dimethylsilyl)aniline,N-phenyl-N-dimethylsilylaniline, and N,N-dimethyl-N-dimethylsilylamine);and mixtures thereof. Tertiary aromatic alkylamines, particularly thosehaving at least one electron-withdrawing group on the aromatic ring,have been found to provide especially good shelf stability. Good shelfstability has also been obtained using amines that are solids at roomtemperature. Good photosensitivity has been obtained using amines thatcontain one or more julolidinyl moieties.

Preferred amide electron donor compounds include N,N-dimethylacetamide,N,N-diethylacetamide, N-methyl-N-phenylacetamide,hexamethylphosphoramide, hexaethylphosphoramide,hexapropylphosphoramide, trimorpholinophosphine oxide,tripiperidinophosphine oxide, and mixtures thereof.

Preferred alkylarylborate salts include

-   Ar₃B⁻(n-C₄H₉)N⁺(C₂H₅)₄-   Ar₃B⁻(n-C₄H₉)N⁺(CH₃)₄-   Ar₃B⁻(n-C₄H₉)N⁺(n-C₄H₉)₄-   Ar₃B⁻(n-C₄H₉)Li⁺-   Ar₃B⁻(n-C₄H₉)N⁺(C₆H₁₃)₄-   Ar₃B⁻—(C₄H₉)N⁺(CH₃)₃(CH₂)₂CO₂(CH₂)₂CH₃-   Ar₃B⁻—(C₄H₉)N⁺(CH₃)₃(CH₂)₂OCO(CH₂)₂CH₃-   Ar₃B⁻-(sec-C₄H₉)N⁺(CH₃)₃(CH₂)₂CO₂(CH₂)₂CH₃-   Ar₃B⁻-(sec-C₄H₉)N⁺(C₆H₁₃)₄-   Ar₃B⁻—(C₄H₉)N⁺(C₈H₁₇)₄-   Ar₃B⁻—(C₄H₉)N⁺(CH₃)₄-   (p-CH₃O—C₆H₄)₃B⁻(n-C₄H₉)N⁺(n-C₄H₉)₄-   Ar₃B⁻—(C₄H₉)N⁺(CH₃)₃(CH₂)₂OH-   ArB⁻(n-C₄H₉)₃N⁺(CH₃)₄-   ArB⁻(C₂H₅)₃N⁺(CH₃)₄-   Ar₂B⁻(n-C₄H₉)₂N⁺(CH₃)₄-   Ar₃B⁻(C₄H₉)N⁺(C₄H₉)₄-   Ar₄B⁻N⁺(C₄H₉)₄-   ArB⁻(CH₃)₃N⁺(CH₃)₄-   (n-C₄H₉)₄B⁻N⁺(CH₃)₄-   Ar₃B⁻(C₄H₉)P⁺(C₄H₉)₄    (where Ar is phenyl, naphthyl, substituted (preferably,    fluoro-substituted) phenyl, substituted naphthyl, and like groups    having greater numbers of fused aromatic rings), as well as    tetramethylammonium n-butyltriphenylborate and tetrabutylammonium    n-hexyl-tris(3-fluorophenyl)borate, and mixtures thereof.

Suitable ether electron donor compounds include 4,4′-dimethoxybiphenyl,1,2,4-trimethoxybenzene, 1,2,4,5-tetramethoxybenzene, and the like, andmixtures thereof. Suitable urea electron donor compounds includeN,N′-dimethylurea, N,N-dimethylurea, N,N′-diphenylurea,tetramethylthiourea, tetraethylthiourea, tetra-n-butylthiourea,N,N-di-n-butylthiourea, N,N′-di-n-butylthiourea, N,N-diphenylthiourea,N,N′-diphenyl-N,N′-diethylthiourea, and the like, and mixtures thereof.

Preferred electron donor compounds for free radical-induced reactionsinclude amines that contain one or more julolidinyl moieties,alkylarylborate salts, and salts of aromatic sulfinic acids. However,for such reactions, the electron donor compound can also be omitted, ifdesired (for example, to improve the shelf stability of thephotoreactive composition or to modify resolution, contrast, andreciprocity). Preferred electron donor compounds for acid-inducedreactions include 4-dimethylaminobenzoic acid, ethyl4-dimethylaminobenzoate, 3-dimethylaminobenzoic acid,4-dimethylaminobenzoin, 4-dimethylaminobenzaldehyde,4-dimethylaminobenzonitrile, 4-dimethylaminophenethyl alcohol, and1,2,4-trimethoxybenzene.

(3) Photoinitiators

Suitable photoinitiators (that is, electron acceptor compounds) for thereactive species of the photoreactive compositions are those that arecapable of being photosensitized by accepting an electron from anelectronic excited state of the multiphoton photosensitizer, resultingin the formation of at least one free radical and/or acid. Suchphotoinitiators include iodonium salts (for example, diaryliodoniumsalts), sulfonium salts (for example, triarylsulfonium salts optionallysubstituted with alkyl or alkoxy groups, and optionally having 2,2′ oxygroups bridging adjacent aryl moieties), and the like, and mixturesthereof.

The photoinitiator is preferably soluble in the reactive species and ispreferably shelf-stable (that is, does not spontaneously promotereaction of the reactive species when dissolved therein in the presenceof the photosensitizer and the electron donor compound). Accordingly,selection of a particular photoinitiator can depend to some extent uponthe particular reactive species, photosensitizer, and electron donorcompound chosen, as described above. If the reactive species is capableof undergoing an acid-initiated chemical reaction, then thephotoinitiator is an onium salt (for example, an iodonium or sulfoniumsalt).

Suitable iodonium salts include those described by Palazzotto et al. inU.S. Pat. No. 5,545,676 at column 2, lines 28 through 46. Suitableiodonium salts are also described in U.S. Pat. Nos. 3,729,313,3,741,769, 3,808,006, 4,250,053 and 4,394,403. The iodonium salt can bea simple salt (for example, containing an anion such as Cl⁻, Br⁻, I⁻ orC₄H₅ SO₃ ⁻) or a metal complex salt (for example, containing SbF₆ ⁻, PF₆⁻, BF₄ ⁻, tetrakis(perfluorophenyl)borate, SbF₅ OH⁻ or AsF₆ ⁻). Mixturesof iodonium salts can be used if desired.

Examples of useful aromatic iodonium complex salt photoinitiatorsinclude diphenyliodonium tetrafluoroborate; di(4-methylphenyl)iodoniumtetrafluoroborate; phenyl-4-methylphenyliodonium tetrafluoroborate;di(4-heptylphenyl)iodonium tetrafluoroborate; di(3-nitrophenyl)iodoniumhexafluorophosphate; di(4-chlorophenyl)iodonium hexafluorophosphate;di(naphthyl)iodonium tetrafluoroborate;di(4-trifluoromethylphenyl)iodonium tetrafluoroborate; diphenyliodoniumhexafluorophosphate; di(4-methylphenyl)iodonium hexafluorophosphate;diphenyliodonium hexafluoroarsenate; di(4-phenoxyphenyl)iodoniumtetrafluoroborate; phenyl-2-thienyliodonium hexafluorophosphate;3,5-dimethylpyrazolyl-4-phenyliodonium hexafluorophosphate;diphenyliodonium hexafluoroantimonate; 2,2′-diphenyliodoniumtetrafluoroborate; di(2,4-dichlorophenyl)iodonium hexafluorophosphate;di(4-bromophenyl)iodonium hexafluorophosphate;di(4-methoxyphenyl)iodonium hexafluorophosphate;di(3-carboxyphenyl)iodonium hexafluorophosphate;di(3-methoxycarbonylphenyl)iodonium hexafluorophosphate;di(3-methoxysulfonylphenyl)iodonium hexafluorophosphate;di(4-acetamidophenyl)iodonium hexafluorophosphate;di(2-benzothienyl)iodonium hexafluorophosphate; and diphenyliodoniumhexafluoroantimonate; and the like; and mixtures thereof. Aromaticiodonium complex salts can be prepared by metathesis of correspondingaromatic iodonium simple salts (such as, for example, diphenyliodoniumbisulfate) in accordance with the teachings of Beringer et al., J. Am.Chem. Soc. 81, 342 (1959).

Preferred iodonium salts include diphenyliodonium salts (such asdiphenyliodonium chloride, diphenyliodonium hexafluorophosphate, anddiphenyliodonium tetrafluoroborate), diaryliodonium hexafluoroantimonate(for example, SarCat™ SR 1012 available from Sartomer Company), andmixtures thereof.

Useful sulfonium salts include those described in U.S. Pat. No.4,250,053 (Smith) at column 1, line 66, through column 4, line 2, whichcan be represented by the formulas:

wherein R₁, R₂, and R₃ are each independently selected from aromaticgroups having from about 4 to about 20 carbon atoms (for example,substituted or unsubstituted phenyl, naphthyl, thienyl, and furanyl,where substitution can be with such groups as alkoxy, alkylthio,arylthio, halogen, and so forth) and alkyl groups having from 1 to about20 carbon atoms. As used here, the term “alkyl” includes substitutedalkyl (for example, substituted with such groups as halogen, hydroxy,alkoxy, or aryl). At least one of R₁, R₂, and R₃ is aromatic, and,preferably, each is independently aromatic. Z is selected from the groupconsisting of a covalent bond, oxygen, sulfur, —S(═O)—, —C(═O)—,—(O═)S(═O)—, and —N(R)—, where R is aryl (of about 6 to about 20carbons, such as phenyl), acyl (of about 2 to about 20 carbons, such asacetyl, benzoyl, and so forth), a carbon-to-carbon bond, or—(R₄—)C(—R₅)—, where R₄ and R₅ are independently selected from the groupconsisting of hydrogen, alkyl groups having from 1 to about 4 carbonatoms, and alkenyl groups having from about 2 to about 4 carbon atoms.X⁻ is an anion, as described below.

Suitable anions, X⁻, for the sulfonium salts (and for any of the othertypes of photoinitiators) include a variety of anion types such as, forexample, imide, methide, boron-centered, phosphorous-centered,antimony-centered, arsenic-centered, and aluminum-centered anions.

Illustrative, but not limiting, examples of suitable imide and methideanions include (C₂F₅SO₂)₂N⁻, (C₄F₉SO₂)₂N⁻, (C₈F₁₇SO₂)₃C⁻, (CF₃SO₂)₃C⁻,(CF₃SO₂)₂N⁻, (C₄F₉SO₂)₃C⁻, (CF₃SO₂)₂(C₄F₉SO₂)C⁻, (CF₃SO₂)(C₄F₉SO₂)N⁻,((CF₃)₂NC₂F₄SO₂)₂N⁻, (CF₃)₂NC₂F₄SO₂C⁻(SO₂CF₃)₂,(3,5-bis(CF₃)C₆H₃)SO₂N⁻SO₂CF₃, C₆H₅SO₂C⁻(SO₂CF₃)₂, C₆H₅SO₂N⁻SO₂CF₃, andthe like. Preferred anions of this type include those represented by theformula (R_(f)SO₂)₃C⁻, wherein R_(f) is a perfluoroalkyl radical havingfrom 1 to about 4 carbon atoms.

Illustrative, but not limiting, examples of suitable boron-centeredanions include F₄B⁻, (3,5-bis(CF₃)C₆H₃)₄B⁻, (C₆F₅)₄B⁻, (p-CF₃C₆H₄)₄B⁻,(m-CF₃C₆H₄)₄B⁻, (p-FC₆H₄)₄B⁻, (C₆F₅)₃(CH₃)B⁻, (C₆F₅)₃(n-C₄H₉)B⁻,(p-CH₃C₆H₄)₃(C₆F₅)B⁻, (C₆F₅)₃FB⁻, (C₆H₅)₃(C₆F₅)B⁻, (CH₃)₂(p-CF₃C₆H₄)₂B⁻,(C₆F₅)₃(n-C₁₈H₃₇O)B⁻, and the like. Preferred boron-centered anionsgenerally contain 3 or more halogen-substituted aromatic hydrocarbonradicals attached to boron, with fluorine being the most preferredhalogen. Illustrative, but not limiting, examples of the preferredanions include (3,5-bis(CF₃)C₆H₃)₄B⁻, (C₆F₅)₄B⁻, (C₆F₅)₃(n-C₄H₉)B⁻,(C₆F₅)₃FB⁻, and (C₆F₅)₃(CH₃)B⁻.

Suitable anions containing other metal or metalloid centers include, forexample, (3,5-bis(CF₃)C₆H₃)₄Al⁻, (C₆F₅)₄Al⁻, (C₆F₅)₂F₄P⁻, (C₆F₅)F₅P⁻,F₆P⁻, (C₆F₅)F₅Sb⁻, F₆Sb⁻, (HO)F₅Sb⁻, and F₆As⁻. The foregoing lists arenot intended to be exhaustive, as other useful boron-centerednonnucleophilic salts, as well as other useful anions containing othermetals or metalloids, will be readily apparent (from the foregoinggeneral formulas) to those skilled in the art.

Preferably, the anion, X⁻, is selected from tetrafluoroborate,hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, andhydroxypentafluoroantimonate (for example, for use withcationically-reactive species such as epoxy resins).

Examples of suitable sulfonium salt photoinitiators include:

-   triphenylsulfonium tetrafluoroborate-   methyldiphenylsulfonium tetrafluoroborate-   dimethylphenylsulfonium hexafluorophosphate-   triphenylsulfonium hexafluorophosphate-   triphenylsulfonium hexafluoroantimonate-   diphenylnaphthylsulfonium hexafluoroarsenate-   tritolysulfonium hexafluorophosphate-   anisyldiphenylsulfonium hexafluoroantimonate-   4-butoxyphenyldiphenylsulfonium tetrafluoroborate-   4-chlorophenyldiphenylsulfonium hexafluorophosphate-   tri(4-phenoxyphenyl)sulfonium hexafluorophosphate-   di(4-ethoxyphenyl)methylsulfonium hexafluoroarsenate-   4-acetonylphenyldiphenylsulfonium tetrafluoroborate-   4-thiomethoxyphenyldiphenylsulfonium hexafluorophosphate-   di(methoxysulfonylphenyl)methylsulfonium hexafluoroantimonate-   di(nitrophenyl)phenylsulfonium hexafluoroantimonate-   di(carbomethoxyphenyl)methylsulfonium hexafluorophosphate-   4-acetamidophenyldiphenylsulfonium tetrafluoroborate-   dimethylnaphthylsulfonium hexafluorophosphate-   trifluoromethyldiphenylsulfonium tetrafluoroborate-   p-(phenylthiophenyl)diphenylsulfonium hexafluoroantimonate-   10-methylphenoxathiinium hexafluorophosphate-   5-methylthianthrenium hexafluorophosphate-   10-phenyl-9,9-dimethylthioxanthenium hexafluorophosphate-   10-phenyl-9-oxothioxanthenium tetrafluoroborate-   5-methyl-10-oxothianthrenium tetrafluoroborate-   5-methyl-10,10-dioxothianthrenium hexafluorophosphate

Preferred sulfonium salts include triaryl-substituted salts such astriarylsulfonium hexafluoroantimonate (for example, SarCat™ SR1010available from Sartomer Company), triarylsulfonium hexafluorophosphate(for example, SarCat™ SR 1011 available from Sartomer Company), andtriarylsulfonium hexafluorophosphate (for example, SarCat™ KI85available from Sartomer Company).

Preferred photoinitiators include iodonium salts (more preferably,aryliodonium salts), sulfonium salts, and mixtures thereof. Morepreferred are aryliodonium salts and mixtures thereof.

Preparation of Photoreactive Composition

The reactive species, multiphoton photosensitizers, electron donorcompounds, and photoinitiators can be prepared by the methods describedabove or by other methods known in the art, and many are commerciallyavailable. These four components can be combined under “safe light”conditions using any order and manner of combination (optionally, withstirring or agitation), although it is sometimes preferable (from ashelf life and thermal stability standpoint) to add the photoinitiatorlast (and after any heating step that is optionally used to facilitatedissolution of other components). Solvent can be used, if desired,provided that the solvent is chosen so as to not react appreciably withthe components of the composition. Suitable solvents include, forexample, acetone, dichloromethane, and acetonitrile. The reactivespecies itself can also sometimes serve as a solvent for the othercomponents.

The three components of the photoinitiator system are present inphotochemically effective amounts (as defined above). Generally, thecomposition can contain at least about 5% (preferably, at least about10%; more preferably, at least about 20%) up to about 99.79%(preferably, up to about 95%; more preferably, up to about 80%) byweight of one or more reactive species; at least about 0.01%(preferably, at least about 0.1%; more preferably, at least about 0.2%)up to about 10% (preferably, up to about 5%; more preferably, up toabout 2%) by weight of one or more photosensitizers; optionally, up toabout 10% (preferably, up to about 5%) by weight of one or more electrondonor compounds (preferably, at least about 0.1%; more preferably, fromabout 0.1% to about 5%); and from about 0.1% to about 10% by weight ofone or more electron acceptor compounds (preferably, from about 0.1% toabout 5%) based upon the total weight of solids (that is, the totalweight of components other than solvent).

A wide variety of adjuvants can be included in the photoreactivecompositions, depending upon the desired end use. Suitable adjuvantsinclude solvents, diluents, resins, binders, plasticizers, pigments,dyes, inorganic or organic reinforcing or extending fillers (atpreferred amounts of about 10% to 90% by weight based on the totalweight of the composition), thixotropic agents, indicators, inhibitors,stabilizers, ultraviolet absorbers, and the like. The amounts and typesof such adjuvants and their manner of addition to the compositions willbe familiar to those skilled in the art.

It is within the scope of this invention to include nonreactivepolymeric binders in the compositions in order, for example, to controlviscosity and to provide film-forming properties. Such polymeric binderscan generally be chosen to be compatible with the reactive species. Forexample, polymeric binders that are soluble in the same solvent that isused for the reactive species, and that are free of functional groupsthat can adversely affect the course of reaction of the reactivespecies, can be utilized. Binders can be of a molecular weight suitableto achieve desired film-forming properties and solution rheology (forexample, molecular weights between about 5,000 and 1,000,000 Daltons;preferably between about 10,000 and 500,000 Daltons; more preferably,between about 15,000 and 250,000 Daltons). Suitable polymeric bindersinclude, for example, polystyrene, poly(methyl methacrylate),poly(styrene)-co-(acrylonitrile), cellulose acetate butyrate, and thelike.

Prior to exposure, the resulting photoreactive compositions can becoated on a substrate, if desired, by any of a variety of coatingmethods known to those skilled in the art (including, for example, knifecoating and spin coating). The substrate can be chosen from a widevariety of films, sheets, and other surfaces (including silicon wafersand glass plates), depending upon the particular application and themethod of exposure to be utilized. Preferred substrates are generallysufficiently flat to enable the preparation of a layer of photoreactivecomposition having a uniform thickness. For applications where coatingis less desirable, the photoreactive compositions can alternatively beexposed in bulk form.

Exposure System and its Use

In carrying out the process of the invention, a photoreactivecomposition can be exposed to light under conditions such thatmultiphoton absorption occurs, thereby causing a region of differentialsolubility characteristics (for example, lesser or greater solubility ina particular solvent) as compared to the photoreactive composition priorto exposure. Such exposure can be accomplished by any known meanscapable of achieving sufficient intensity of the light.

One exemplary type of system that can be used is shown in FIG. 1.Referring to FIG. 1, fabrication system 10 includes light source 12,optical system 14 comprising a final optical element 15 (optionallyincluding galvo-mirrors and a telescope to control beam divergence), andmoveable stage 16. Stage 16 is moveable in one, two, or, more typically,three dimensions. Substrate 18 mounted on stage 16 has a layer 20 ofphotoreactive composition 24 thereon. Light beam 26 originating fromlight source 12 passes through optical system 14 and leaves throughfinal optical element 15 which focuses it to a point P within layer 20,thereby controlling the three-dimensional spatial distribution of lightintensity within the composition and causing at least a portion ofphotoreactive composition 24 in the vicinity of point P to become more,or less, soluble in at least one solvent than it was immediately priorto exposure to light beam 26.

By moving stage 16, or by directing light beam 26 (for example, moving alaser beam using galvo-mirrors and a telescope) in combination withmoving one or more elements of optical system 14, the focal point P canbe scanned or translated in a three-dimensional pattern that correspondsto a desired shape. The resulting reacted or partially reacted portionof photoreactive composition 24 then creates a three-dimensionalstructure of the desired shape. For example, in a single pass thesurface profile (corresponding to a thickness of about one volume pixelor voxel) of one or more light extraction structures can be exposed orimaged, which upon development can form the surface of the structure(s).

The imagewise exposing of the surface profile can be carried out byscanning at least the perimeter of a planar slice of a desiredthree-dimensional structure and then scanning a plurality of preferablyparallel, planar slices to complete the structure. Slice thickness canbe controlled to achieve a sufficiently low level of surface roughnessto provide optical quality light extraction structures. For example,smaller slice thicknesses can be desirable in regions of greaterstructure taper to aid in achieving high structure fidelity, but largerslice thicknesses can be utilized in regions of less structure taper toaid in maintaining useful fabrication times. In this way, a surfaceroughness less than the slice thickness (preferably, less than aboutone-half of the slice thickness; more preferably, less than aboutone-quarter of the slice thickness) can be achieved without sacrificingfabrication speed (throughput or number of structures fabricated perunit time).

When the photoreactive composition is coated on a substrate thatexhibits a degree of non-planarity that is of the same or greater sizemagnitude as voxel height, it can be desirable to compensate for thenon-planarity to avoid optically- or physically-defective structures.This can be accomplished by locating (for example, using a confocalinterface locator system, interferometry, or fluorescence interfacelocator system) the position of the interface between the substrate andthe portion of the photoreactive composition that is to be exposed, andthen adjusting the location of the optical system 14 appropriately tofocus light beam 26 at the interface. (Such a procedure is described indetail in a co-pending and co-filed patent application bearing Appl. No.60/752,529, the description of which is incorporated herein byreference.) Preferably, this procedure can be followed for at least onestructure out of every twenty structures in an array (more preferably,at least one out of every ten; most preferably, for each structure inthe array).

Light source 12 can be any light source that produces sufficient lightintensity to effect multiphoton absorption. Suitable sources include,for example, femtosecond near-infrared titanium sapphire oscillators(for example, those available from Coherent, Santa Clara, Calif., underthe trade designation “MIRA OPTIMA 900-F”) pumped by an argon ion laser(for example, those available from Coherent under the trade designation“INNOVA”). This laser, operating at 76 MHz, has a pulse width of lessthan 200 femtoseconds, is tunable between 700 and 980 nm, and hasaverage power up to 1.4 Watts. Another useful laser is available fromSpectra-Physics, Mountain View, Calif., under the trade designation “MAITAI”, tunable to wavelengths in a range of from 750 to 850 nanometers,and having a repetition frequency of 80 megahertz, and a pulse width ofabout 100 femtoseconds (1×10⁻¹³ sec), with an average power level up to1 Watt.

However, any light source (for example, a laser) that providessufficient intensity to effect multiphoton absorption at a wavelengthappropriate for the multiphoton absorber used in the photoreactivecomposition can be utilized. Such wavelengths can generally be in therange of about 300 to about 1500 nm; preferably, from about 400 to about1100 nm; more preferably, from about 600 to about 900 nm; morepreferably, from about 750 to about 850 nm, inclusive. Typically, thelight fluence (for example, peak intensity of a pulsed laser) is greaterthan about 10⁶ W/cm². The upper limit on the light fluence is generallydictated by the ablation threshold of the photoreactive composition. Forexample, Q-switched Nd:YAG lasers (for example, those available fromSpectra-Physics under the trade designation “QUANTA-RAY PRO”), visiblewavelength dye lasers (for example, those available from Spectra-Physicsunder the trade designation “SIRAH” pumped by a Q-switched Nd:YAG laserfrom Spectra-Physics having the trade designation “Quanta-Ray PRO”), andQ-switched diode pumped lasers (for example, those available fromSpectra-Physics under the trade designation “FCBAR”) can also beutilized.

Preferred light sources are near infrared pulsed lasers having a pulselength less than about 10⁻⁸ second (more preferably, less than about10⁻⁹ second; most preferably, less than about 10⁻¹¹ second). Other pulselengths can be used as long as the peak intensity and ablation thresholdcriteria above are met. Pulsed radiation can, for example, have a pulsefrequency of from about one kilohertz up to about 50 megahertz, or evenmore. Continuous wave lasers can also be used.

Optical system 14 can include, for example, refractive optical elements(for example, lenses or microlens arrays), reflective optical elements(for example, retroreflectors or focusing mirrors), diffractive opticalelements (for example, gratings, phase masks, and holograms), polarizingoptical elements (for example, linear polarizers and waveplates),dispersive optical elements (for example, prisms and gratings),diffusers, Pockels cells, waveguides, and the like. Such opticalelements are useful for focusing, beam delivery, beam/mode shaping,pulse shaping, and pulse timing. Generally, combinations of opticalelements can be utilized, and other appropriate combinations will berecognized by those skilled in the art. Final optical element 15 caninclude, for example, one or more refractive, reflective, and/ordiffractive optical elements. In one embodiment, an objective such as,for example, those used in microscopy can be conveniently obtained fromcommercial sources such as, for example, Carl Zeiss, North America,Thornwood, N.Y., and used as final optical element 15. For example,fabrication system 10 can include a scanning confocal microscope (forexample, those available from Bio-Rad Laboratories, Hercules, Calif.,under the trade designation “MRC600”) equipped with a 0.75 numericalaperture (NA) objective (such as, for example, those available from CarlZeiss, North America under the trade designation “20X FLUAR”).

It can often be desirable to use optics with relatively large numericalaperture to provide highly-focused light. However, any combination ofoptical elements that provides a desired intensity profile (and spatialplacement thereof) can be utilized.

Exposure times generally depend upon the type of exposure system used tocause reaction of the reactive species in the photoreactive composition(and its accompanying variables such as numerical aperture, geometry oflight intensity spatial distribution, the peak light intensity duringthe laser pulse (higher intensity and shorter pulse duration roughlycorrespond to peak light intensity)), as well as upon the nature of thephotoreactive composition. Generally, higher peak light intensity in theregions of focus allows shorter exposure times, everything else beingequal. Linear imaging or “writing” speeds generally can be about 5 to100,000 microns/second using a laser pulse duration of about 10⁻⁸ to10⁻¹⁵ second (for example, about 10⁻¹¹ to 10⁻¹⁴ second) and about 10² to10⁹ pulses per second (for example, about 10³ to 10⁸ pulses per second).

In order to facilitate solvent development of the exposed photoreactivecomposition and obtain a fabricated light extraction structure, athreshold dose of light (that is, threshold dose) can be utilized. Thisthreshold dose is typically process specific, and can depend onvariables such as, for example, the wavelength, pulse frequency,intensity of the light, the specific photoreactive composition, thespecific structure being fabricated, or the process used for solventdevelopment. Thus, each set of process parameters can typically becharacterized by a threshold dose. Higher doses of light than thethreshold can be used, and can be beneficial, but higher doses (onceabove the threshold dose) can typically be used with a slower writingspeed and/or higher light intensity.

Increasing the dose of light tends to increase the volume and aspectratio of voxels generated by the process. Thus, in order to obtainvoxels of low aspect ratio, it is generally preferable to use a lightdose that is less than about 10 times the threshold dose, preferablyless than about 4 times the threshold dose, and more preferably lessthan about 3 times the threshold dose. In order to obtain voxels of lowaspect ratio, the radial intensity profile of light beam 26 ispreferably Gaussian.

Through multiphoton absorption, light beam 26 induces a reaction in thephotoreactive composition that produces a volume region of materialhaving solubility characteristics different from those of the unexposedphotoreactive composition. The resulting pattern of differentialsolubility can then be realized by a conventional development process,for example, by removing either exposed or unexposed regions.

The exposed photoreactive composition can be developed, for example, byplacing the exposed photoreactive composition into solvent to dissolveregions of higher solvent solubility, by rinsing with solvent, byevaporation, by oxygen plasma etching, by other known methods, and bycombinations thereof. Solvents that can be used for developing theexposed photoreactive composition include aqueous solvents such as, forexample, water (for example, having a pH in a range of from 1 to 12) andmiscible blends of water with organic solvents (for example, methanol,ethanol, propanol, acetone, acetonitrile, dimethylformamide,N-methylpyrrolidone, and the like, and mixtures thereof); and organicsolvents. Exemplary useful organic solvents include alcohols (forexample, methanol, ethanol, and propanol), ketones (for example,acetone, cyclopentanone, and methyl ethyl ketone), aromatics (forexample, toluene), halocarbons (for example, methylene chloride andchloroform), nitriles (for example, acetonitrile), esters (for example,ethyl acetate and propylene glycol methyl ether acetate), ethers (forexample, diethyl ether and tetrahydrofuran), amides (for example,N-methylpyrrolidone), and the like, and mixtures thereof.

An optional bake after exposure to light under multiphoton absorptionconditions, but prior to solvent development, can be useful for somephotoreactive compositions such as, for example, epoxy-type reactivespecies. Typical bake conditions include temperatures in a range of fromabout 40° C. to about 200° C., for times in a range of from about 0.5minutes to about 20 minutes.

Optionally, after exposure of only the surface profile of a lightextraction structure array, preferably followed by solvent development,a nonimagewise exposure using actinic radiation can be carried out toeffect reaction of the remaining unreacted photoreactive composition.Such a nonimagewise exposure can preferably be carried out by using aone-photon process.

Complex three-dimensional light extraction structures and lightextraction structure arrays can be prepared in this manner.

Light Extraction Structure Arrays

The process of the invention can be used to flexibly and controllablyprovide arrays comprising light extraction structures of a variety ofsizes and geometric configurations or surface profiles (including, forexample, both protruding and recessed structures). The process can beparticularly well-suited, however, for providing light extractionstructure arrays exhibiting at least some variation in at least oneshape factor as a function of position within the array and/orexhibiting a non-uniform distribution of light extraction structures.For example, arrays exhibiting a controlled spatial variation of lightextraction structure height and/or spacing across the array can beuseful for modifying the uniformity and efficiency of light extraction.

For example, the process can be used to fabricate arrays comprisinglight extraction structures having heights of protruding structures (ordepths of recessed structures) in the range of about 5 microns to about300 microns (preferably, about 50 to about 200; more preferably, about75 to about 150) and/or maximum lengths and/or maximum widths in therange of about 5 microns to about 500 microns (preferably, about 50 toabout 300; more preferably, about 100 to about 300). A wide range offill factors (up to 100 percent) can be achieved. For many applications,fill factors of about 1 percent to 100 percent (preferably, about 5percent to about 75 percent) can be useful.

Light extraction structures having various geometric configurations (forexample, cones, aspheres, truncated aspheres, and truncated cones, where“truncated” configurations have both a base and a second truncation thatcan form a planar top surface) can be fabricated with array fill factorsup to 100 percent. The configurations can be complex (for example,combining segments of multiple shapes in a single structure, such as astacked combination of an asphere and a pyramid or a cone). Preferredgeometric configurations include those that are both truncated andsymmetrical (for example, truncated cones, truncated aspheres, andcombinations thereof).

Geometric configurations can comprise such structural elements as abase, one or more faces (for example, that form a side wall), and a top(which can be, for example, a planar surface (for example, formed bytruncation) or even a point). Such elements can be of essentially anyshape (for example, bases, faces, and tops can be circular, elliptical,or polygonal (regular or irregular), and the resulting side walls can becharacterized by a vertical cross section (taken perpendicular to thebase) that is parabolic, hyperbolic, or linear in nature, or acombination thereof). Preferably, the side wall is not perpendicular tothe base of the structure (for example, vertical tangent angles at thebase of about 10 degrees to about 80 degrees (preferably, about 20 toabout 70; more preferably, about 30 to about 60) can be useful). Thelight extraction structure can have a principal axis connecting thecenter of its top with the center of its base. Tilt angles (the anglebetween the principal axis and the base) of up to about 80 degrees(preferably, up to about 25 degrees) can be achieved, depending upon thedesired brightness and field of view.

The process of the invention can be used to fabricate patterned orrandom, heterogeneous light extraction structure array masterforms withmultiple structure designs in a single writing process. Average surfaceroughnesses of λ/2 (preferably, λ/4; more preferably, λ/10; mostpreferably, λ/20) can be achieved (where λ (lambda) is the wavelength oflight for which the structure is designed; hereinafter the “operatingwavelength”).

The fill factor of the arrays can be varied to control brightness anduniformity. The packing arrangement or distribution of the structurescan be regular (for example, square or hexagonal) or irregular. Theshape factors of the structures comprising the array can also varythroughout the array. For example, the heights can be varied accordingto the distance of a particular structure from a light source (toachieve uniform light extraction). To maintain continuously uniformlight output (and minimize or eliminate bright spots), arrays exhibitingan irregular variation in shape factor and/or areal density can beprepared. Preferably, both areal density and at least one shape factorvary across the array (more preferably, both vary and at least onevaries irregularly). As used herein, “regular variation” means changingby a defined (for example, mathematically prescribed) amount (forexample, linearly, exponentially, or according to a power series) perunit distance across the array.

The process of the invention can also be used to fabricate arrayscomprising at least two light extraction structures that havenon-parallel principal axes (hereinafter, termed “tilted structure”arrays). Such arrays can exhibit an independent variation in tilt anglefrom structure to structure across the array.

Thus, a preferred light extraction structure array comprises a pluralityof light extraction structures having a non-uniform distribution, eachlight extraction structure having a principal axis and at least oneshape factor, and the plurality exhibiting a variation in areal density,in at least one shape factor, and in principal axis across the pluralityof light extraction structures. (More preferably, the geometricconfiguration of at least one light extraction structure is selectedfrom truncated cones, truncated aspheres, and combinations thereof,and/or the variation exhibited by the plurality is irregular across theplurality for at least one of areal density, shape factor, and principalaxis.) Such arrays can be useful, for example, for directing extractedlight in multiple directions, in accordance with the variation inprincipal axis across the plurality of light extraction structures.

Another preferred light extraction structure array comprises a pluralityof light extraction structures having a non-uniform distribution, eachof the light extraction structures having a geometric configuration, andthe geometric configuration of at least one light extraction structurebeing a truncated asphere. (More preferably, the geometric configurationof each light extraction structure in the array is selected fromaspheres, truncated aspheres, and combinations thereof.) Such arrays canbe useful, for example, for achieving uniform extracted light outputwithout the appearance of discrete bright spots or lines (which canresult from approaches that involve only a reduction in light extractionstructure density in regions of the array that are relatively close to alight source). Uniformity of output can be achieved without such brightspots, for example, by maintaining a relatively high density of lightextraction structures (for example, having a spacing of less than about200 micrometers; preferably, less than about 150 micrometers), as wellas reducing light extraction structure efficiency through truncation, inthe regions of the array that are relatively close to the light source.

Preparation of Replication Tool from Master

A replication tool, such as a mold insert, can be prepared by using alight extraction structure array prepared as described above as amaster. That is, another material can be placed against the master toprepare a mold insert having the negative image of the array. The mastercan then be removed, leaving a mold insert that can subsequently be usedto prepare additional arrays. The mold insert will have cavities in theshape of the negative image of the array. A metal replication tool canbe made from a master by electroplating or electroforming a metal, suchas nickel, against the master and subsequently removing the master. Asilicone replication tool can be made by curing a silicone resin againstthe master and subsequently removing the master.

Light Guides and Optical Devices

Light guides comprising the light extraction structure arrays of theinvention can be fabricated from a wide variety of optically suitablematerials including polycarbonates; polyacrylates such as polymethylmethacrylate; polystyrene; and glass; with high refractive indexmaterials such as polyacrylates and polycarbonates being preferred. Thelight guides preferably are made by molding, embossing, curing, orotherwise forming an injection moldable resin against theabove-described replication tool. Most preferably, a cast and curetechnique is utilized. Methods for molding, embossing, or curing thelight guide will be familiar to those skilled in the art. Coatings (forexample, reflective coatings of thin metal) can be applied to at least aportion of one or more surfaces of the light guides (for example, to theinterior or recessed surface of light extraction structures) by knownmethods, if desired. Individual light guide designs can, if desired, beevaluated without the need for actual fabrication by using suitableray-tracing modeling software such as “ASAP” from Breault ResearchOrganization, Inc., “Code V” and “Light Tools” from Optical ResearchAssociates, Inc., “Rayica” from the Optica Software Division of i-CytMission Technology, Inc., “Trace Pro” from Lambda Research, Inc., and“ZEMAX” from Zemax Development Corporation.

The light guides of the present invention can be especially useful inbacklit displays (for example, comprising a light source, a light gatingdevice (for example, a liquid crystal display (LCD)), and a light guide)and keypads (for example, comprising a light source, an array ofpressure-sensitive switches at least a portion of which transmits light,and a light guide). The light guides are useful as point to area or lineto area back light guides for subminiature or miniature display orkeypad devices illuminated with light emitting diodes (LEDs) powered bysmall batteries. Suitable display devices include color or monochromeLCD devices for cell phones, pagers, personal digital assistants,clocks, watches, calculators, laptop computers, vehicular displays, andthe like. Other display devices include flat panel displays such aslaptop computer displays or desktop flat panel displays. Suitablebacklit keypad devices include keypads for cell phones, pagers, personaldigital assistants, calculators, vehicular displays, and the like

In addition to LEDs, other suitable light sources for displays andkeypads include fluorescent lamps (for example, cold cathode fluorescentlamps), incandescent lamps, electroluminescent lights, and the like. Thelight sources can be mechanically held in any suitable manner in slots,cavities, or openings machined, molded, or otherwise formed in lighttransition areas of the light guides. Preferably, however, the lightsources are embedded, potted, or bonded in the light transition areas inorder to eliminate any air gaps or air interface surfaces between thelight sources and surrounding light transition areas, thereby reducinglight loss and increasing the light output emitted by the light guide.Such mounting of the light sources can be accomplished, for example, bybonding the light sources in the slots, cavities, or openings in thelight transition areas using a sufficient quantity of a suitableembedding, potting, or bonding material. The slots, cavities, oropenings can be on the top, bottom, sides, or back of the lighttransition areas. Bonding can also be accomplished by a variety ofmethods that do not incorporate extra material, for example, thermalbonding, heat staking, ultrasonic welding, plastic welding, and thelike. Other methods of bonding include insert molding and casting aroundthe light source(s).

EXAMPLES

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention. Unless otherwisenoted, all procedures were carried out under a dry nitrogen atmospherewith dry and deoxygenated solvents and reagents. Unless otherwise noted,all solvents and reagents were or can be obtained from Aldrich ChemicalCo., Milwaukee, Wis.

As used herein,

“SR1012” refers to diaryliodonium hexafluoroantimonate, obtained fromSartomer Co., Inc., Exton, Pa.; and

“Strippable SU-8” refers to SU-8XP KMPR epoxy negative photoresistobtained from MicroChem Corp., Newton, Mass.;

“SU-8” refers to SU-8 2150 epoxy negative photoresist obtained fromMicroChem. Corp., Newton, Mass.

Example 1 Fabrication of a Light Extraction Structure Array

A circular silicon wafer (10.2 cm (4 inches) in diameter; obtained fromWafer World, Inc., West Palm Beach, Fla.) was cleaned by soaking it forapproximately ten minutes in a 3:1 volume/volume (v/v) mixture ofconcentrated sulfuric acid and 30 weight percent aqueous hydrogenperoxide. The wafer was then rinsed with deionized water and then withisopropanol, after which it was dried under a stream of air. The waferwas then spin-coated with XP OmniCoat primer (MicroChem. Corp., Newton,Mass.) at 500 revolutions per minute (RPM) for 5 seconds followed by2700 RPM for 25 seconds. The wafer was then placed on a hot plate at200° C. for 1 minute to dry.

A concentrated solution of photosensitizer dyeN,N,N-tris(7-(2-benzothiazolyl)-9,9-diethyl-2-fluorenyl)amine (describedalong with its synthesis in Example 20 of U.S. Pat. No. 6,300,502(Kannan et al.)) and SR1012 in cyclopentanone (available from LancasterSynthesis, Windham, N.H.) was prepared. The solution was syringedthrough a 0.2 micrometer (μm) polytetrafluoroethylene (PTFE) filtercartridge and was added to Strippable SU-8 to make a solution of 0.5percent (%) photosensitizer dye and 1.0% SR-1012 (based upon totalweight of solids). The resulting solution was then filtered through a1.0 μm glass fiber filter and then a 0.7 μm glass fiber filter.

The filtered solution was poured into a 5 cm×5 cm (inside dimensions)area masked with a green gasket tape on the primed silicon wafer. Thewafer was allowed to dry at room temperature over the weekend and wasthen placed in a forced air oven for 30 minutes at 65° C., followed by90 minutes at 95° C., followed by 30 minutes at 65° C. to afford acoated silicon wafer with a substantially solvent-free (hereinafter,“dry”) coating thickness of approximately 300 μm.

The backside of the wafer was cleaned with isopropyl alcohol to removeany debris. The wafer was then mounted on a porous carbon vacuum chuck(flatness greater than 1 μm). A two-photon fabrication system was thenactivated to produce an optical signal that was stationary in thevertical position (the fabrication system was not activating thez-control to move the signal in the vertical direction). The signal wasused as a detection mechanism to produce a reflection off of the wafersurface in conjunction with a confocal microscope system such that theonly condition that would produce a confocal response would occur whenthe optical signal was focused on the surface of the wafer. The systemwas aligned to the interface between the coating of photosensitivematerial and the wafer in the vertical direction.

Two-photon polymerization of the dry coating was carried out in thefollowing manner, using a diode-pumped Ti:sapphire laser(Spectra-Physics, Mountain View, Calif.) operating at a wavelength of800 nm, nominal pulse width of 80 fs, pulse repetition rate of 80 MHz,and average power of approximately 1 W. The coated wafer was placed on acomputer-controllable three-axis stage (obtained from Aerotech, Inc.,Pittsburgh, Pa.). The laser beam was attenuated by neutral densityfilters and was focused into the dry coating using a galvoscanner withtelescope for x, y, and z-axis control (available from NutfieldTechnology, Inc., Windham, N.H.) and a lens (Nikon CFI Plan Achromat 50Xoil objective N.A. 0.90, working distance 0.400 mm, 4.0 mm focallength), which was applied directly on the surface of the dry coating.The average power was measured at the output of the objective lens usinga wavelength-calibrated photodiode (obtained from Ophir Optronics, Ltd.,Wilmington, Mass.) and was determined to be approximately 9 mW.

A software file that was produced using a CAD program (AUTODESK INVENTORavailable from Autodesk, San Raphael, Calif.) and that described atruncated cone structure was then loaded into the laser scanningsoftware of the two-photon fabrication system. The scanning softwaresliced the prescribed structure into planes with a vertical separationsufficiently small to result in a final polymerized array of structureswith low surface roughness. The slice thickness was chosen in thesoftware to be 500 nm, and each planar slice was cross-hatched withhatch spacing of 2 microns to provide an approximately fully curedstructure. The system was then activated to scan the laser beam topolymerize the coating of photosensitive material to define thetruncated cone structures. The system was operated in an automatedfashion to place light extraction structures (in the form of truncatedcones) at prescribed positions (corresponding to the positions ofpressure-sensitive switches (buttons) associated with a cellphonekeypad), using a software model that optimized the structure locationsfor optimum light extraction uniformity and efficiency. The distributionof the resulting array, as well as that of each cluster of structurescorresponding to the button positions, was non-uniform. Followingimaging on the two-photon laser scanner, the photosensitive material wascured at 95 degrees C. The resulting cured array was subsequentlydeveloped using MicroChem SU-8 developer for approximately 90 minutes.FIG. 2 shows a scanning electron micrograph of a side view of a portionof the resulting developed array.

Example 2 Fabrication of a Light Extraction Structure Array

A circular silicon wafer (10.2 cm (4 inches) in diameter; obtained fromWafer World, Inc., West Palm Beach, Fla.) was spin-coated with XPOmniCoat primer (MicroChem. Corp., Newton, Mass.) at 500 revolutions perminute (RPM) for 5 seconds followed by 2700 RPM for 25 seconds. Thewafer was then placed on a hot plate at 200° C. for 1 minute to dry.

A concentrated solution of photosensitizer dyeN,N,N-tris(7-(2-benzothiazolyl)-9,9-diethyl-2-fluorenyl)amine (describedalong with its synthesis in Example 20 of U.S. Pat. No. 6,300,502(Kannan et al.)) and SR1012 in cyclopentanone (available from LancasterSynthesis, Windham, N.H.) was prepared. The solution was syringedthrough a 0.2 micrometer (μm) polytetrafluoroethylene (PTFE) filtercartridge and was added to SU-8 to make a solution of 0.5 percent (%)photosensitizer dye and 1.0% SR-1012 (based upon total weight ofsolids). The resulting solution was then filtered through a 1.0 μm glassfiber filter and then a 0.7 μm glass fiber filter. The filtered solutionwas coated onto the silicon wafer by spin coating, followed by removalof solvent at 80° C. for 10 minutes, to yield a dry coating thickness ofabout 30 μm.

The backside of the wafer was cleaned with isopropyl alcohol to removeany debris. The wafer was then mounted on a porous carbon vacuum chuck(flatness less than 1 μm). A two-photon fabrication system was thenactivated to produce an optical signal that was stationary in thevertical position (the fabrication system was not activating thez-control to move the signal in the vertical direction). The signal wasused as a detection mechanism to produce a reflection off of the wafersurface in conjunction with a confocal microscope system such that theonly condition that would produce a confocal response would occur whenthe optical signal was focused on the surface of the wafer. The systemwas aligned to the interface between the coating of photosensitivematerial and the wafer in the vertical direction.

Two-photon polymerization of the dry coating was carried out in thefollowing manner, using a diode-pumped Ti:sapphire laser(Spectra-Physics, Mountain View, Calif.) operating at a wavelength of800 nm, nominal pulse width of 80 fs, pulse repetition rate of 80 MHz,and average power of approximately 1 W. The coated wafer was placed on acomputer-controllable three-axis stage (obtained from Aerotech, Inc.,Pittsburgh, Pa.). The laser beam was attenuated by neutral densityfilters and was focused into the dry coating using a galvoscanner withtelescope for x, y, and z-axis control (available from NutfieldTechnology, Inc., Windham, N.H.) and a lens (Nikon CFI Plan Achromat 50Xoil objective N.A. 0.90, working distance 0.400 mm, 4.0 mm focallength), which was applied directly on the surface of the dry coating.The average power was measured at the output of the objective lens usinga wavelength-calibrated photodiode (obtained from Ophir Optronics, Ltd.,Wilmington, Mass.) and was determined to be approximately 16 mW.

A software file that was produced using a CAD program (AUTODESK INVENTORavailable from Autodesk, San Raphael, Calif.) and that described atruncated asphere structure for regions relatively close to alight-emitting diode (LED) light source and a non-truncated aspherestructure for the region farthest away from the LED light source) wasthen loaded into the laser scanning software of the two-photonfabrication system. The scanning software sliced the prescribedstructure into planes with a vertical separation sufficiently small toresult in a final polymerized array of structures with low surfaceroughness. The slice thickness was chosen in the software to be 500 nm,and each planar slice was cross-hatched with hatch spacing of 2 micronsto provide an approximately fully cured structure. The system was thenactivated to scan the laser beam to polymerize the coating ofphotosensitive material to define the structures. The system wasoperated in an automated fashion to place light extraction structures(in the form of truncated and non-truncated aspheres) at prescribedpositions (described below) using a software model that optimized thestructure locations for optimum light extraction uniformity andefficiency. The distribution of the resulting array was non-uniform.

The light extraction structure array comprised aspheres (paraboloidshaving a base radius of 40 microns and a height of 8 microns) andtruncated aspheres. There were 3 regions of light extraction structures,each region having a different areal density (which increased withincreasing distance from the LED) and shape factor (height and/orgeometric configuration). Each region was a 10 millimeter (mm) square.On a global coordinate system, using an (X,Y) coordinate space, thelower righthand corner of Region 1 was located at (15 mm, -5 mm), thelower righthand corner of Region 2 was located at (5 mm, -5 mm), and thelower righthand corner of Region 3 was located at (−5 mm, −5 mm). Thesource LED was located at (20 mm, 0 mm), with emission in the negative Xdirection.

The height of the light extraction structures (truncated aspheres) inRegion 1 was 5 microns and in Region 2 was 6 microns. There was notruncation of the light extraction structures (aspheres) in Region 3.

The areal density of each region of the resulting array can be describedby a uniform spacing (s_(y)) between light extraction structures in theY direction and a non-uniform spacing (s_(xi)) between light extractionstructures (i+1) and (i) in the X direction, which varied according tothe formula s_(x(i))=s_(y)((i+1)^(p)−i^(p)) where i is the number of thelight extraction structure (beginning with the number 0 for the firststructure located at the righthand side of the region and incrementingby one for each structure to the left of it thereafter). Region 1 hads_(y)=555 micrometers and p=0.6542; Region 2 had s_(y)=263 micrometersand p=0.7948; and Region 3 had s_(y)=149 micrometers and p=0.8948.

Following imaging on the two-photon laser scanner, the photosensitivematerial was cured at 95 degrees C. for 15 minutes. The resulting curedarray was subsequently developed using MicroChem SU-8 developer forapproximately 10 minutes and dried to form a master tool.

A silicone (GE RTV 615 2-part silicone, General Electric Co, Waterford,N.Y.) was cast on the master tool, which had sandblasting tape arrangedaround the light extraction structure array to form a dam about 3 mmthick corresponding to the outline of a final lightguide. The siliconewas degassed in a vacuum oven for 15 minutes, a release liner was addedon top of the silicone, and the silicone was cured at 80° C. for 1½hours. The silicone was removed from the master tool to form a daughtertool. A dam about 3 mm high was constructed around the silicone daughtertool using sandblasting tape, and an ultraviolet (UV) curable acrylate(Photomer 6210, Cognis, Cincinnati, Ohio) was poured over the siliconedaughter tool and degassed 15 minutes in a vacuum oven at 50° C. Thedegassed construction was covered with a release liner and cured bypassing under a UV light (H bulb, Fusion UV Systems, Gaithersburg, Md.)5 times at 12 centimeters per second (24 feet/minute). The resultingcured acrylate was separated from the silicone to form amicroreplication tool. A dam was formed around the microreplication toolusing sandblasting tape (about 2 mm), and the tool was filled with asilicone (GE RTV 615 2-part silicone). The silicone was degassed for 15minutes in a vacuum oven, covered with a film, and cured for 1½ hours at80° C. The resulting cured silicone was removed from the tool to form asilicone lightguide (refractive index of 1.41) with light extractionstructures (aspheres and truncated aspheres) patterned into one side.The lightguide edges were at X=−20 mm, X=20 mm, Y=−30 mm, and Y=30 mm,with reference to the above-described coordinate system. The base ofeach aspherical light extraction structure was located on the bottomsurface of the lightguide, and the asphere extended into the lightguideby the amount of its height. The truncated aspherical light extractionstructures comprised aspheres whose extension into the lightguide wasterminated by a plane parallel to the asphere base.

The silicone lightguide was placed on a white sheet of paper (to reflectlight refracted downward out of the light extraction structures backinto the lightguide) and was coupled with a single white LED connectedto a power supply. The lightguide was viewed from its top surface andshowed relatively uniform light intensity with essentially no brightspots (as observed by eye) across all regions.

The referenced descriptions contained in the patents, patent documents,and publications cited herein are incorporated by reference in theirentirety as if each were individually incorporated. Variousunforeseeable modifications and alterations to this invention willbecome apparent to those skilled in the art without departing from thescope and spirit of this invention. It should be understood that thisinvention is not intended to be unduly limited by the illustrativeembodiments and examples set forth herein and that such examples andembodiments are presented by way of example only.

1. A process comprising (a) providing a photoreactive composition, saidphotoreactive composition comprising (1) at least one reactive speciesthat is capable of undergoing an acid- or radical-initiated chemicalreaction, and (2) at least one multiphoton photoinitiator system; and(b) imagewise exposing at least a portion of said composition to lightsufficient to cause simultaneous absorption of at least two photons,thereby inducing at least one acid- or radical-initiated chemicalreaction where said composition is exposed to the light, said imagewiseexposing being carried out in a pattern that is effective to define atleast the surface of an array of light extraction structures, each saidlight extraction structure having at least one shape factor, and saidarray of light extraction structures having a distribution that isuniform or non-uniform; wherein said imagewise exposing is carried outby scanning at least the perimeter of a plurality of planar slices of adesired three-dimensional light extraction structure, while controllingslice thickness so as to achieve a light extraction structure surfaceroughness of less than the slice thickness.
 2. The process of claim 1,wherein said process further comprises developing said composition byremoving the resulting exposed portion, or the resulting non-exposedportion, of said composition.
 3. The process of claim 1, wherein, afterimagewise exposing at least a portion of said composition, said processfurther comprises nonimagewise exposing at least a portion of saidcomposition to light sufficient to effect reaction of at least a portionof any remaining unreacted photoreactive composition.
 4. The process ofclaim 1, wherein said shape factor is selected from height, length,width, and geometric configuration.
 5. The process of claim 1, whereinat least one said shape factor of at least one said light extractionstructure is different from the corresponding shape factor of at leastone other said light extraction structure.
 6. The process of claim 1,wherein said distribution is non-uniform.
 7. The process of claim 1,wherein said distribution is non-uniform, and wherein at least one saidshape factor varies across said array.
 8. The process of claim 1,wherein the areal density of said array of light extraction structuresvaries across said array and/or at least one shape factor varies acrosssaid array.
 9. The process of claim 1, wherein at least a majority ofsaid light extraction structures have a height of less than 300 microns,a length or width of less than 500 microns, and an average surfaceroughness of less than half the operating wavelength.
 10. The process ofclaim 1, wherein said array has a fill factor in the range of 5 to 75percent.
 11. The process of claim 1, wherein at least two said lightextraction structures have non-parallel principal axes.
 12. The processof claim 1, wherein said reactive species is a curable species.
 13. Theprocess of claim 1, wherein said reactive species is a non-curablespecies.
 14. The process of claim 1, wherein said multiphotonphotoinitiator system comprises photochemically effective amounts of (a)at least one multiphoton photosensitizer that is capable ofsimultaneously absorbing at least two photons; (b) optionally, at leastone electron donor compound different from said multiphotonphotosensitizer and capable of donating an electron to an electronicexcited state of said photosensitizer; and (c) at least onephotoinitiator that is capable of being photosensitized by accepting anelectron from an electronic excited state of said photosensitizer,resulting in the formation of at least one free radical and/or acid. 15.The process of claim 1, wherein said process comprises providing saidphotoreactive composition on a substrate and locating the interfacebetween said composition and said substrate.
 16. The process of claim 1,wherein said controlling slice thickness comprises varying slicethickness.
 17. The process of claim 1, wherein said process comprises anonimagewise exposure that is carried out using a one-photon process.18. The process of claim 1, wherein said array comprises a masterform,and said masterform is used to fabricate a tool for replication.
 19. Aprocess comprising (a) providing a photoreactive composition, saidphotoreactive composition comprising (1) at least one curable speciesthat is capable of undergoing an acid- or radical-initiated chemicalreaction, and (2) at least one multiphoton photoinitiator systemcomprising photochemically effective amounts of (i) a multiphotonphotosensitizer having a two-photon absorption cross-section greaterthan that of fluorescein; (ii) optionally, at least one electron donorselected from alkylarylborate salts, tertiary aromatic alkylamines, andmixtures thereof; and (iii) at least one photoinitiator selected fromiodonium salts, sulfonium salts, and mixtures thereof; (b) imagewiseexposing at least a portion of said composition to light sufficient tocause simultaneous absorption of at least two photons, thereby inducingat least one acid-or radical-initiated chemical reaction where saidcomposition is exposed to the light, said imagewise exposing beingcarried out in a pattern that is effective to define at least thesurface of an array of light extraction structures, each said lightextraction structure having at least one shape factor selected fromheight, length, width, and geometric configuration, said array of lightextraction structures having a distribution that is non-uniform, andsaid array of light extraction structures exhibiting a variation ofareal density and/or at least one said shape factor across said array;and (c) developing said composition by removing at least a portion ofthe resulting non-exposed portion of said composition; wherein saidimagewise exposing is carried out by scanning at least the perimeter ofa plurality of planar slices of a desired three-dimensional lightextraction structure, while controlling slice thickness so as to achievea light extraction structure surface roughness of less than the slicethickness.
 20. A light extraction structure array comprising a pluralityof light extraction structures having a non-uniform distribution, eachsaid light extraction structure having a principal axis and at least oneshape factor, and said plurality of light extraction structuresexhibiting a variation in areal density, in at least one said shapefactor, and in said principal axis across said plurality; wherein atleast a majority of said light extraction structures have an averagesurface roughness of less than half the operating wavelength.
 21. Alight extraction structure array comprising a plurality of lightextraction structures having a non-uniform distribution, each said lightextraction structure having a geometric configuration, and saidgeometric configuration of at least one said light extraction structurebeing a truncated asphere.
 22. A light guide comprising the lightextraction structure array of claim
 20. 23. A light guide comprising thelight extraction structure array of claim
 21. 24. An optical devicecomprising the light guide of claim
 22. 25. An optical device comprisingthe light guide of claim 23.